CN114634431A - 一种含硫醚和砜基取代的烯烃类化合物的合成方法 - Google Patents
一种含硫醚和砜基取代的烯烃类化合物的合成方法 Download PDFInfo
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- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/64—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton
- C07C323/65—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton containing sulfur atoms of sulfone or sulfoxide groups bound to the carbon skeleton
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- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/30—Hetero atoms other than halogen
- C07D333/34—Sulfur atoms
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- C07C2602/00—Systems containing two condensed rings
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- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
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Abstract
本发明公开了一种含硫醚和砜基取代的烯烃类化合物的合成方法,以式(1)所示的化合物和式(2)所示的化合物为反应原料,在路易斯碱催化作用下,在有机溶剂中,在有碱或无碱的反应条件下进行反应,反应结束后进行处理得到如式(3)所示的含硫醚和砜基取代的烯烃类化合物,反应式如下所示:式中:R1选自含有烷基、甲氧基或卤素原子的取代苯环、噻吩、萘基、联苯基或樟脑烷基;R2选自氘代甲基、含酰胺侧链的酯基、烷基、苯甲基、硝基取代的苄基、溴取代的直链烷烃;R3选自苄基、苯乙基、二苯基甲基或己基,R4选自苯基或含有烷基的取代苯环。本发明收率高,选择性高;反应条件温和;反应原料简单易得、价格便宜、性状稳定、无刺激性气味,环保。
Description
技术领域
本发明属于有机合成技术领域,具体涉及一种含硫醚和砜基取代的烯烃类化合物的合成方法。
背景技术
含硫醚或砜基取代的烯烃类化合物是一类非常重要的化合物,其广泛存在于药物、农药、配体和有机化工产品中(如下所示),因此从一些结构简单、商业易得的化合物中构建含硫醚和砜基取代的双官能烯烃类化合物显得尤为重要,含硫醚和砜基取代的双官能烯烃类化合物以及应用如下:
含硫醚和砜基取代的双官能烯烃类化合物已经建立了许多实用的路线如:[3+2]环化加成、β-加成、γ-加成等。与构建其他含双官能团化合物的众多方法相比,形成含硫醚和砜基取代的双官能烯烃类化合物的方法仍不发达。现有的方法通常需要化学计量的金属试剂或额外的步骤来制备,且反应成本高,环境友好性差、底物适用范围狭窄。鉴于含硫醚和砜基取代的双官能烯烃类化合物的重要性及其有限的合成路线,发展一种底物适用范围广泛、催化剂便宜易获得且能得到专一构型含硫醚和砜基取代的双官能烯烃类化合物的方法是非常有必要的。
发明内容
针对上述问题,本发明的目的在于提供一种含硫醚和砜基取代的烯烃类化合物的合成方法,本发明研究发现联烯酸酯或联烯酮是一类常用于构建双官能化合物的化合物,它们具有稳定、易制备、价格便宜等特点。
为达到上述目的,提出以下技术方案:
本发明提出一种含硫醚和砜基取代的烯烃类化合物,其结构如式(3)所示,
其中,R1选自取代苯环、烷烃、杂环、萘基、联苯基或樟脑烷基;
R2选自取代苯环、氘代甲基、酯基、含取代基的苄基、直链烷烃
R3选自苄基、苯乙基、二苯基甲基、直链烷烃;
优选地,R1选自烷基、甲氧基或卤素的取代苯环、噻吩、萘基、联苯基或樟脑烷基;
R2选自烷基的取代苯环、直链烷烃、氘代甲基或不饱和脂肪烃、取代烷烃、含取代基的苄基;
R3选自苄基、苯乙基、二苯基甲基、C1-C6烷烃;
优选地,R1选自甲基、甲氧基、叔丁基、氟原子、氯原子、溴原子的取代苯环、噻吩基、联苯基、萘基或樟脑烷基;
R2选自甲基、叔丁基的取代苯环、C1-C12烷烃、氘代甲基、1-丙烯基、1-丙炔基、含酰胺侧链的酯基、硝基取代的苄基、溴取代的直链烷烃;
R3选自苄基、苯乙基、二苯基甲基、己基;
本发明提出了一种含硫醚和砜基取代的烯烃类化合物的合成方法,在路易斯碱催化条件下,以式(1)所示的硫代硫酸盐与式(2)所示的联烯酸脂为反应原料,在有机溶剂中,一定的温度下反应,有效地实现了相应转化,得到所述式(3)所示的含硫醚和砜基取代的烯烃类化合物。
其中,所述反应过程如下所示:
R1选自甲基、甲氧基、叔丁基、氟原子、氯原子、溴原子的取代苯环、噻吩基、联苯基、萘基;
R2选自甲基、叔丁基的取代苯环、C1-C12烷烃、氘代甲基、1-丙烯基、1-丙炔基、含酰胺侧链的酯基、硝基取代的苄基、溴取代的直链烷烃;
R3选自苄基、苯乙基、二苯基甲基、己基;
如以上反应式所示,本发明利用式(1)所示的硫代硫酸盐与式(2)所示的联烯酸酯为反应原料,在路易斯碱催化作用下,在反应溶剂中反应得到如式(3)所示含硫醚和砜基取代的烯烃类化合物。
进一步地,所述起始原料式(1)所示的硫代硫酸盐和式(2)所示的联烯酸酯用量的摩尔比例为1.0:1.2-1.0:2.0,优选地,两者用量的摩尔比例为1.0:1.5。
进一步地,所述路易斯碱催化剂是DABCO、PPh3、DMAP、Quinine,优选地,所述路易斯碱催化剂是DABCO,所述催化剂的用量为式(1)所示硫代硫酸盐的1-15mol%,优选地所述催化剂的用量为原料式(1)所示的硫代硫酸盐的10mol%。
进一步地,所述有机溶剂是二氯甲烷、乙酸乙酯、氯仿、二甲亚砜、N,N-二甲基甲酰胺、乙腈、四氢呋喃。优选地,为二氯甲烷。
进一步地,所述反应是在-50-0℃进行的,优选地,反应的温度为-30℃。
本发明还提出了按照本发明上述合成方法制备得到的如式(3)所示的碳氮轴手性磺酰胺类化合物。
本发明提出一种含硫醚和砜基取代的烯烃类化合物,其结构如式(6)所示,
其中,R1选自取代苯环、苯基;
优选地R1选自烷基取代苯环、苯基;
优选地R1选自甲氧基、甲基取代苯环、苯基;
本发明提出了一种含硫醚和砜基取代的烯烃类化合物的合成方法,在路易斯碱催化条件下,以式(4)所示的氘代甲基试剂与式(5)所示的联烯酮为反应原料,在有机溶剂中,一定的温度下反应,有效地实现了相应转化,得到所述式(6)所示的含硫醚和砜基取代的烯烃类化合物。
其中,所述反应过程如下所示:
其中,R1选自取代苯环、苯基;
优选地R1选自烷基取代苯环、苯基;
优选地R1选自甲氧基、甲基取代苯环、苯基;
如以上反应式所示,本发明利用式(4)所示的氘代甲基试剂与式(5)所示的联烯酮为反应原料,在路易斯碱催化作用下,在反应溶剂中反应得到如式(6)所示含硫醚和砜基取代的烯烃类化合物。
进一步地,所述起始原料式(4)所示的氘代甲基试剂和式(2)所示的联烯酸酯用量的摩尔比例为1.0:1.2-1.0:2.0,优选地,两者用量的摩尔比例为1.0:1.5。
进一步地,所述路易斯碱催化剂是DABCO、PPh3、DMAP、Quinine,优选地,所述路易斯碱催化剂是DABCO,所述催化剂的用量为式(4)所示的氘代甲基试剂的1-15mol%,优选地所述催化剂的用量为原料式(4)所示的氘代甲基试剂的10mol%。
进一步地,所述有机溶剂是二氯甲烷、乙酸乙酯、氯仿、二甲亚砜、N,N-二甲基甲酰胺、乙腈、四氢呋喃,优选地,为二氯甲烷。
进一步地,所述反应是在-70-0℃进行的,优选地,反应的温度为-50℃。
本发明还提出了按照本发明上述合成方法制备得到的如式(6)所示含硫醚和砜基取代的烯烃类化合物。
本发明提出一种含硫醚和砜基取代的烯烃类化合物,其结构如式(7)所示,
其中,R1选自取代苯环;
R2选自直链烷烃、氘代烷烃;
R3选自苄基、苯乙基、二苯基甲基、直链烷烃;
优选地,R1选自烷基的取代苯环;
R2选自C1-C12直链烷烃、氘代直链烷烃;
R3选自苄基、苯乙基、二苯基甲基、C1-C6烷烃;
优选地,R1选自甲基、甲氧基、叔丁基的取代苯环;
R2选自甲基、C12烷烃、氘代甲基;
R3选自苄基、苯乙基、二苯基甲基、己基;
本发明提出了一种含硫醚和砜基取代的烯烃类化合物的合成方法,在路易斯碱催化条件下,以式(1)所示的硫代硫酸盐与式(2)所示的联烯酸脂为反应原料,在有机溶剂中,一定的温度下反应,有效地实现了相应转化,得到所述式(7)所示的含硫醚和砜基取代的烯烃类化合物。
其中,所述反应过程如下所示:
其中,R1选自取代苯环;
R2选自直链烷烃、氘代烷烃;
R3选自苄基、苯乙基、二苯基甲基、直链烷烃;
优选地,R1选自烷基的取代苯环;
R2选自C1-C12直链烷烃、氘代直链烷烃;
R3选自苄基、苯乙基、二苯基甲基、C1-C6烷烃;
优选地,R1选自甲基、甲氧基、叔丁基的取代苯环;
R2选自甲基、C12烷烃、氘代甲基;
R3选自苄基、苯乙基、二苯基甲基、己基;
进一步地,所述起始原料式(1)所示的硫代硫酸盐和式(2)所示的联烯酸酯用量的摩尔比例为1.0:1.2-1.0:2.0,优选地,两者用量的摩尔比例为1.0:1.5。
进一步地,所述路易斯碱催化剂是DABCO、PPh3、DMAP、Quinine,优选地,所述路易斯碱催化剂是DABCO,所述催化剂的用量为式(1)所示的硫代硫酸盐的1-15mol%,优选地所述催化剂的用量为原料式(1)所示的硫代硫酸盐的10mol%。
进一步地,所述碱是DBU、i-Pr2Net,优选地,所述碱为DBU,所述碱的用量为原料式(1)的1.0-3.0当量,优选地,所述碱的用量为原料式(1)的2.0当量。
进一步地,所述有机溶剂是二氯甲烷、乙酸乙酯、氯仿、二甲亚砜、N,N-二甲基甲酰胺、乙腈、四氢呋喃。优选地,为二氯甲烷。
进一步地,所述反应是在-30-0℃进行的。优选地,反应的温度为-30℃。
本发明的有益效果在于:a)反应收率高,高效,选择性高;b)反应条件温和,可在空气条件下进行反应;c)反应原料简单易得、价格便宜、性状稳定、无刺激性气味;d)催化剂廉价易得且用量少,经济实用,对环境友好;e)反应溶剂为有机溶剂,绿色无毒;本发明以制备简便的联烯酮或者联烯酯碳酸酯为反应原料,在路易斯碱做催化剂的催化作用下,反应得构型专一的含硫醚和砜基取代的烯烃类化合物,本发明所得的含硫醚和砜基取代的烯烃类化合物具有较高的衍生空间可作为生物活性化合物、药物的结构砌块。
具体实施方式
结合以下具体实施例,对本发明作进一步的详细说明,本发明的保护内容不局限于以下实施例。在不背离发明构思的精神和范围下,本领域技术人员能够想到的变化和优点都被包括在本发明中,并且以所附的权利要求书为保护范围。实施本发明的过程、条件、试剂、实验方法等,除以下专门提及的内容之外,均为本领域的普遍知识和公知常识,本发明没有特别限制内容。以下实施例所给出的数据包括具体操作和反应条件及产物,产物纯度通过核磁鉴定。
表1本发明的新的含硫醚和砜基取代的烯烃类化合物
实施例1
化合物3a的合成:
空气氛围下,在烧瓶中加入1a(0.2mmol,40.4mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2a(0.3mmol,52.2mg,1.5equiv.),反应10小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物3a(产率91%)。(洗脱剂极性:石油醚/乙酸乙酯15:1)。1H NMR(400MHz,CDCl3)δ7.69(d,J=8.3Hz,2H),7.34–7.27(m,3H),7.25–7.19(m,4H),6.63(s,1H),6.36(s,1H),4.99(d,J=12.3Hz,1H),4.93(d,J=12.3Hz,1H),4.26(s,1H),2.36(s,3H),1.94(s,3H).;13C NMR(100MHz,CDCl3)δ168.1,145.7,144.8,135.6,134.9,129.8,128.7,128.5,128.4,128.3,128.0,67.5,45.8,21.6,15.0.;HRMS(ESI-TOF)Calcdfor[C19H20O4S2,M+Na]+399.0695;Found:399.0696.
实施例2
化合物3b的合成:
空气氛围下,在烧瓶中加入1b(0.2mmol,41.6mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2a(0.3mmol,52.2mg,1.5equiv.),反应10小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物3b(产率92%)。(洗脱剂极性:石油醚/乙酸乙酯15:1)。1H NMR(400MHz,CDCl3)δ7.66(d,J=8.3Hz,2H),7.30–7.24(m,3H),7.21–7.16(m,4H),6.60(s,1H),6.33(s,1H),4.95(d,J=12.3Hz,1H),4.90(d,J=12.3Hz,1H),4.22(s,1H),2.33(s,3H).;13C NMR(100MHz,CDCl3)δ168.1,145.7,144.9,135.6,135.0,129.8,128.7,128.5,128.4,128.4,128.0,67.5,45.7,21.6.;HRMS(ESI-TOF)Calcdfor[C19H17D3O4S2,M+Na]+405.1118,Fund:405.1118.
实施例3
化合物3c的合成:
空气氛围下,在烧瓶中加入1c(0.2mmol,44.3mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2a(0.3mmol,52.2mg,1.5equiv.),反应10小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物3c(产率85%)。(洗脱剂极性:石油醚/乙酸乙酯15:1)。1H NMR(400MHz,CDCl3)δ7.74(d,J=8.9Hz,2H),7.33–7.27(m,3H),7.24–7.20(m,2H),6.89(d,J=8.9Hz,2H),6.61(s,1H),6.34(s,1H),5.00(d,J=12.3Hz,1H),4.94(d,J=12.3Hz,1H),4.26(s,1H),3.80(s,3H).;13C NMR(100MHz,CDCl3)δ168.2,163.9,146.0,135.0,130.7,129.9,128.5,128.4,128.2,128.0,114.4,67.6,55.6,45.8.;HRMS(ESI-TOF)Calcd for[C19H17D3O5S2,M+Na]+418.0833,Found:418.0835.
实施例4
化合物3d的合成:
空气氛围下,在烧瓶中加入1d(0.2mmol,49.5mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2a(0.3mmol,52.2mg,1.5equiv.),反应10小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物3d(产率85%)。(洗脱剂极性:石油醚/乙酸乙酯10:1)。1H NMR(400MHz,CDCl3)δ7.75(d,J=8.6Hz,2H),7.47(d,J=8.6Hz,2H),7.34–7.26(m,3H),7.24–7.20(m,2H),6.63(d,J=0.6Hz,1H),6.37(s,1H),4.97(d,J=12.4Hz,1H),4.90(d,J=12.4Hz,1H),4.27(s,1H),1.27(s,9H).;13C NMR(100MHz,CDCl3)δ168.0,157.8,145.8,135.4,135.0,128.7,128.5,128.3,128.3,127.9,126.2,67.4,45.9,35.2,30.9.;HRMS(ESI-TOF)Calcd for[C22H23D3O4S2,M+Na]+444.1353,Found:444.1354.
实施例5
化合物3e的合成:
空气氛围下,在烧瓶中加入1e(0.2mmol,41.9mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2a(0.3mmol,52.2mg,1.5equiv.),反应10小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物3e(产率87%)。(洗脱剂极性:石油醚/乙酸乙酯15:1)。1H NMR(400MHz,CDCl3)δ7.81–7.77(m,2H),7.30–7.26(m,3H),7.20–7.18(m,2H),7.08–7.03(m,2H),6.63(s,1H),6.38(s,1H),4.97(d,J=12.2Hz,1H),4.93(d,J=12.2Hz,1H),4.23(s,1H).;13C NMR(100MHz,CDCl3)δ168.0,165.8(d,1JC-F=255Hz),145.4,134.8(d,4JC-F=3Hz),134.7,131.3,131.2,128.9(d,2JC-F=83Hz),128.5,128.1,116.4(d,3JC-F=22Hz),67.6,45.6;19F NMR(376MHz,CDCl3)δ-102.7;HRMS(ESI-TOF)Calcd for[C18H14D3FO4S2,M+Na]+406.0633,Found:406.0637.
实施例6
化合物3f的合成:
空气氛围下,在烧瓶中加入1f(0.2mmol,45.1mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2a(0.3mmol,52.2mg,1.5equiv.),反应10小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物3f(87%)。(洗脱剂极性:石油醚/乙酸乙酯15:1)。1HNMR(400MHz,CDCl3)δ7.69(d,J=8.4Hz,2H),7.34(d,J=8.4Hz,2H),7.27(d,J=5.8Hz,3H),7.20–7.15(m,2H),6.62(s,1H),6.38(s,1H),4.95(d,J=12.3Hz,1H),4.90(d,J=12.3Hz,1H),4.22(s,1H).;13C NMR(100MHz,CDCl3)δ167.9,145.3,140.5,137.3,134.8,129.8,129.7,129.5,128.6,128.5,128.1,67.7,45.6.;HRMS(ESI-TOF)Calcd for[C18H14D3ClO4S2,M+Na]+422.0337,Found:422.0337.
实施例7
化合物3g的合成:
空气氛围下,在烧瓶中加入1g(0.2mmol,54.0mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2a(0.3mmol,52.2mg,1.5equiv.),反应10小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物3g(产率84%)。(洗脱剂极性:石油醚/乙酸乙酯15:1)。1H NMR(400MHz,CDCl3)δ7.64(d,J=8.5Hz,2H),7.53(d,J=8.5Hz,2H),7.33–7.27(m,3H),7.22–7.18(m,2H),6.65(s,1H),6.40(s,1H),4.97(d,J=12.3Hz,1H),4.92(d,J=12.2Hz,1H),4.24(s,1H).;13C NMR(101MHz,CDCl3)δ167.9,145.1,137.7,134.7,132.4,129.8,129.7,129.2,128.5,128.5,128.1,67.6,45.5.;HRMS(ESI-TOF)Calcd for[C18H14D3BrO4S2,M+Na]+444.0013,Found:444.0017.
实施例8
化合物3h的合成:
空气氛围下,在烧瓶中加入1b(0.2mmol,41.6mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2b(0.3mmol,75.1mg,1.5equiv.),反应10小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物3h(产率87%)。(洗脱剂极性:石油醚/乙酸乙酯20:1)。1H NMR(400MHz,CDCl3)δ7.69(d,J=8.3Hz,2H),7.32–7.27(m,5H),7.26–7.19(m,5H),7.17(d,J=8.1Hz,2H),6.65(s,1H),6.64(s,1H),6.34(s,1H),4.40(s,1H),2.35(s,3H).;13C NMR(100MHz,CDCl3)δ167.1,145.7,144.8,139.2,139.2,135.6,129.8,128.7,128.4,128.4,128.1,128.0,127.0,126.9,78.4,77.3,45.7,21.6.;HRMS(ESI-TOF)Calcd for[C25H21D3O4S2,M+Na]+478.1197,Found:478.1198.
实施例9
化合物3i的合成:
空气氛围下,在烧瓶中加入1b(0.2mmol,41.6mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2c(0.3mmol,56.5mg,1.5equiv.),反应10小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物3i(产率76%)。(洗脱剂极性:石油醚/乙酸乙酯15:1)。1H NMR(600MHz,CDCl3)δ7.74(d,J=8.1Hz,2H),7.34–7.29(m,4H),7.28–7.24(m,1H),7.20(d,J=7.5Hz,2H),6.67(s,1H),6.37(s,1H),4.26(s,1H),4.23–4.16(m,2H),2.87(t,J=7.0Hz,2H),2.43(s,3H).;13C NMR(100MHz,CDCl3)δ168.1,145.7,144.8,137.2,135.6,129.7,128.8,128.5,128.4,126.6,66.2,45.8,34.6,21.5.;HRMS(ESI-TOF)Calcd for[C20H19D3O4S2,M+Na]+416.1040,Found:416.1040.
实施例10
化合物3j的合成:
空气氛围下,在烧瓶中加入1b(0.2mmol,41.6mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2d(0.3mmol,50.4mg,1.5equiv.),反应10小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物3j(86%)。(洗脱剂极性:石油醚/乙酸乙酯15:1)。1HNMR(400MHz,CDCl3)δ7.69(d,J=8.2Hz,2H),7.26(d,J=8.1Hz,2H),6.62(s,1H),6.35(s,1H),4.18(s,1H),3.94–3.82(m,2H),2.37(s,3H),1.49–1.40(m,2H),1.22(d,J=14.9Hz,6H),0.82(t,J=6.8Hz,3H).;13C NMR(100MHz,CDCl3)δ168.3,145.8,144.8,135.6,129.8,128.6,128.5,66.1,45.8,31.2,28.2,25.3,22.4,21.6,13.9.;HRMS(ESI-TOF)Calcd for[C18H23D3O4S2,M+Na]+396.1353,Found;396.1355.
实施例11
化合物3k的合成:
空气氛围下,在烧瓶中加入1h(0.2mmol,74.5mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2a(0.3mmol,52.2mg,1.5equiv.),反应10小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物3k(产率89%)。(洗脱剂极性:石油醚/乙酸乙酯15:1)。1H NMR(400MHz,CDCl3)δ7.73(d,J=8.9Hz,2H),7.38–7.27(m,3H),7.25–7.17(m,2H),6.89(d,J=8.9Hz,2H),6.62(s,1H),6.38(s,1H),4.99(d,J=12.4Hz,1H),4.91(d,J=12.4Hz,1H),4.26(s,1H),3.80(s,3H),2.47–2.29(m,2H),1.39–1.13(m,20H),0.84(t,J=6.8Hz,3H).;13C NMR(100MHz,CDCl3)δ168.5,163.8,146.5,135.0,130.7,129.7,128.5,128.3,128.0,114.4,67.5,55.6,44.9,32.5,31.9,29.6,29.5,29.4,29.3,29.0,28.6,28.6,22.6,14.1.;HRMS(ESI)Calcd for[C30H42O5S2,M+Na]+569.2366,Found:569.2371.
实施例12
化合物3l的合成:
空气氛围下,在烧瓶中加入1i(0.2mmol,69.7mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2a(0.3mmol,52.2mg,1.5equiv.),反应10小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物3l(产率89%)。(洗脱剂极性:石油醚/乙酸乙酯20:1)。1H NMR(400MHz,CDCl3)δ7.68–7.64(m,2H),7.37–7.32(m,3H),7.31–7.27(m,2H),7.08–7.04(m,1H),6.73(s,1H),6.47(s,1H),5.07(d,J=12.3Hz,1H),5.02(d,J=12.3Hz,1H),4.42(s,1H),2.54–2.38(m,2H),1.47–1.38(m,2H),1.23(d,J=17.0Hz,18H),0.88(t,J=6.7Hz,3H).;13C NMR(100MHz,CDCl3)δ168.5,146.7,139.6,135.1,135.0,134.9,129.2,128.5,128.4,128.2,127.9,67.7,44.8,32.6,31.9,29.6,29.5,29.5,29.3,29.0,28.6,28.6,22.6,14.1.;HRMS(ESI-TOF)Calcd for[C27H38O4S3,M+Na]+545.1824,Found:545.1824.
实施例13
化合物3l的合成:
空气氛围下,在烧瓶中加入1j(0.2mmol,83.7mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2a(0.3mmol,52.2mg,1.5equiv.),反应10小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物3m(产率90%)。(洗脱剂极性:石油醚/乙酸乙酯20:1)。1H NMR(400MHz,CDCl3)δ7.81(d,J=8.4Hz,2H),7.57(d,J=8.4Hz,2H),7.46(d,J=7.3Hz,2H),7.40–7.30(m,3H),7.23–7.16(m,3H),7.16–7.10(m,2H),6.64(s,1H),6.39(s,1H),4.91(d,J=12.3Hz,1H),4.83(d,J=12.3Hz,1H),4.24(s,1H),2.39–2.22(m,2H),1.29–1.22(m,2H),1.19–1.02(m,18H),0.77(t,J=6.8Hz,3H).;13C NMR(100MHz,CDCl3)δ168.5,146.6,146.2,138.8,137.0,134.9,129.4,129.1,129.0,128.7,128.5,128.4,128.0,127.7,127.3,67.6,44.9,32.5,31.9,29.6,29.5,29.4,29.3,29.0,28.6,28.6,22.6,14.1.;HRMS(ESI)Calcd for[C35H44O4S2,M+Na]+615.2573,Found:615.2574.
实施例14
化合物3n的合成:
空气氛围下,在烧瓶中加入1k(0.2mmol,68.5mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2a(0.3mmol,52.2mg,1.5equiv.),反应10小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物3n(产率87%)。(洗脱剂极性:石油醚/乙酸乙酯10:1)。1H NMR(400MHz,CDCl3)δ7.75(d,J=8.4Hz,2H),7.47(d,J=8.4Hz,2H),7.34–7.27(m,3H),7.23(d,J=7.7Hz,2H),6.66(s,1H),6.41(s,1H),4.97(d,J=12.4Hz,1H),4.88(d,J=12.4Hz,1H),4.28(s,1H),2.43–2.26(m,2H),1.31(d,J=3.3Hz,2H),1.27(s,9H),1.23–1.11(m,10H),0.83(t,J=6.9Hz,3H).;13C NMR(100MHz,CDCl3)δ168.4,157.8,146.3,135.4,135.0,128.9,128.5,128.3,128.3,127.9,126.2,67.4,44.9,35.2,32.4,31.6,30.9,29.0,28.9,28.5,28.5,22.5,14.0.;HRMS(ESI-TOF)Calcdfor[C29H40O4S2,M+Na]+539.2260,Fund:539.2260.
实施例15
化合物3o的合成:
空气氛围下,在烧瓶中加入1l(0.2mmol,64.7mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2a(0.3mmol,52.2mg,1.5equiv.),反应10小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物3o(产率97%)。(洗脱剂极性:石油醚/乙酸乙酯20:1)。1H NMR(400MHz,CDCl3)δ8.03(d,J=8.5Hz,2H),7.59(d,J=8.2Hz,2H),7.38–7.32(m,3H),7.27–7.18(m,6H),6.67(s,1H),6.38(s,1H),5.04(d,J=12.2Hz,1H),4.94(d,J=12.2Hz,1H),4.06(s,1H),3.76(d,J=13.8Hz,1H),3.65(d,J=13.8Hz,1H),2.40(s,3H).;13C NMR(100MHz,CDCl3)δ167.8,146.9,145.4,145.0,143.7,135.0,134.7,129.7,129.1,128.5,128.2,128.1,123.5,67.7,43.9,35.7,21.5.;HRMS(ESI-TOF)Calcd for[C25H23NO6S2,M+Na]+520.0859,Found 520.0860.
实施例16
化合物3p的合成:
空气氛围下,在烧瓶中加入1m(0.2mmol,64.6mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2a(0.3mmol,52.2mg,1.5equiv.),反应10小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物3p(产率85%)。(洗脱剂极性:石油醚/乙酸乙酯15:1)。1H NMR(400MHz,CDCl3)δ7.65(d,J=8.0Hz,2H),7.30–7.25(m,3H),7.23–7.15(m,4H),6.61(s,1H),6.35(s,1H),4.95(d,J=12.3Hz,1H),4.87(d,J=12.3Hz,1H),4.22(s,1H),3.20(t,J=6.6Hz,2H),2.43–2.29(m,5H),1.72–1.63(m,2H),1.53–1.39(m,2H).;13C NMR(101MHz,CDCl3)δ168.3,146.1,145.0,135.4,134.9,129.8,129.0,128.5,128.4,128.4,128.1,67.6,44.6,32.7,31.4,31.2,26.9,21.6.;HRMS(ESI-TOF)Calcd for[C22H25BrO4S2,M+Na]+519.0270,Found:519.0271.
实施例17
化合物3q的合成:
空气氛围下,在烧瓶中加入1n(0.2mmol,45.7mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2a(0.3mmol,52.2mg,1.5equiv.),反应10小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物3q(产率85%)。(洗脱剂极性:石油醚/乙酸乙酯20:1)。1H NMR(400MHz,CDCl3)δ7.68(d,J=8.3Hz,2H),7.35–7.26(m,3H),7.26–7.18(m,4H),6.63(s,1H),6.37(s,1H),5.55–5.43(m,1H),5.02–4.85(m,4H),4.19(s,1H),3.11–2.93(m,2H),2.36(s,3H).;13C NMR(101MHz,CDCl3)δ168.4,146.2,144.8,135.4,134.9,132.0,129.7,128.9,128.5,128.4,128.3,127.9,118.8,67.5,43.6,35.3,21.5.;HRMS(ESI-TOF)Calcd for[C21H22O4S2,M+Na]+425.0852,Found:425.0853.
实施例18
化合物3r的合成:
空气氛围下,在烧瓶中加入1o(0.2mmol,45.3mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2a(0.3mmol,52.2mg,1.5equiv.),反应10小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物3r(产率97%)。(洗脱剂极性:石油醚/乙酸乙酯20:1)。1H NMR(400MHz,CDCl3)δ7.67(d,J=8.3Hz,2H),7.29–7.23(m,3H),7.19(d,J=8.3Hz,4H),6.58(s,1H),6.28(s,1H),4.98(d,J=12.3Hz,1H),4.93(d,J=12.3Hz,1H),4.50(s,1H),3.16(d,J=16.8,2.6Hz,1H),3.03(dd,J=16.8,2.6Hz,1H),2.31(s,3H),2.07(t,J=2.6Hz,1H).;13C NMR(100MHz,CDCl3)δ167.9,145.8,144.9,135.4,134.8,129.8,129.1,128.5,128.4,128.3,128.0,77.9,72.4,67.7,44.8,21.5,20.2.;HRMS(ESI-TOF)Calcd for[C21H20O4S2,M+Na]+423.0695,Found:425.0695.
实施例19
化合物3s的合成:
空气氛围下,在烧瓶中加入1p(0.2mmol,55.7mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2a(0.3mmol,52.2mg,1.5equiv.),反应10小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物3s(产率45%)。(洗脱剂极性:石油醚/乙酸乙酯20:1)。1H NMR(400MHz,CDCl3)δ7.71(d,J=8.2Hz,2H),7.37–7.30(m,3H),7.27(s,1H),7.25(s,1H),7.19(dd,J=6.4,2.8Hz,2H),7.05(d,J=8.1Hz,2H),6.98(d,J=8.0Hz,2H),6.65(s,1H),6.33(s,1H),4.99(d,J=12.3Hz,1H),4.91(d,J=12.3Hz,1H),4.58(s,1H),2.42(s,3H),2.30(s,3H).;13C NMR(100MHz,CDCl3)δ13C NMR(100MHz,CDCl3)δ168.1,145.2,144.8,139.2,135.4,134.9,133.9,129.8,129.3,128.5,128.4,128.3,128.1,128.1,67.6,49.0,21.6,21.1.;HRMS(ESI-TOF)Calcd for[C25H24O4S2,M+Na]+475.1008,Found:475.1010.
实施例20
化合物3t的合成:
空气氛围下,在烧瓶中加入1q(0.2mmol,75.1mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2a(0.3mmol,52.2mg,1.5equiv.),反应10小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物3t(88%,1:1dr)。(洗脱剂极性:石油醚/乙酸乙酯6:1)。1H NMR(400MHz,CDCl3)δ7.84(d,J=2.0Hz,2H),7.58–7.55(m,1H),7.45(s,2H),7.32(s,3H),7.21(d,J=2.2Hz,2H),6.66(s,1H),6.37(s,1H),5.23(d,J=8.4Hz,1H),4.98(d,J=12.5Hz,2H),4.45(s,2H),3.68(s,3H),2.89(s,1H),2.83–2.77(m,1H),1.42(s,9H).;13CNMR(100MHz,CDCl3)δ170.6,167.9,154.9,145.9,138.3,134.6,133.8,129.4,129.1,128.4,128.4,128.4,128.1,80.2,67.7,52.8,52.5,45.0,34.2,28.1.;HRMS(ESI-TOF)Calcd for[C26H31NO8S2,M+Na]+572.1383,Fund:572.1388.
实施例21
化合物3u的合成:
空气氛围下,在烧瓶中加入1r(0.2mmol,85.1mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2a(0.3mmol,52.2mg,1.5equiv.),反应10小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物3u(87%,1:1dr)。(洗脱剂极性:石油醚/乙酸乙酯6:1)。1H NMR(400MHz,CDCl3)δ8.42(s,1H),7.87(s,1H),7.80(d,J=4.2Hz,2H),7.67–7.65(m,1H),7.55–7.51(m,2H),7.17–7.13(m,3H),6.97(d,J=1.8Hz,2H),6.66(s,1H),6.34(s,1H),5.22–5.17(m,1H),4.69(t,J=12.1Hz,2H),4.36(s,2H),3.52(s,3H),2.81(d,J=7.9Hz,1H),2.76–2.71(m,1H),1.33(s,9H).;13C NMR(100MHz,CDCl3)δ170.9,168.0,155.0,146.0,135.2,135.1,134.5,132.0,130.7,130.5,129.8,129.6,129.5,128.4,128.4,128.0,127.9,127.73,122.8,80.2,67.8,53.1,52.6,45.1,34.4,28.2.;HRMS(ESI-TOF)Calcd for[C30H33NO8S2,M+Na]+622.1540,Fund:622.1540.
实施例22
化合物3v的合成:
空气氛围下,在烧瓶中加入1s(0.2mmol,89.9mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2a(0.3mmol,52.2mg,1.5equiv.),反应10小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物3v(72%,1:1dr)。(洗脱剂极性:石油醚/乙酸乙酯3:1)。1H NMR(400MHz,CDCl3)δ7.35–7.31(m,5H),6.54(d,1H),6.47(s,1H),5.46(d,J=7.7Hz,1H),5.19(d,J=12.2Hz,2H),4.54(s,2H),3.72(s,3H),3.55(d,J=14.7Hz,1H),3.04–2.94(m,2H),2.91(d,J=14.7Hz,1H),2.39–2.32(m,2H),2.10–2.08(m,2H),1.94(s,1H),1.80–1.73(m,2H),1.42(s,9H),1.07(s,3H),0.81(s,3H).;13C NMR(100MHz,CDCl3)δ214.3,171.1,168.7,155.1,146.5,,134.9,130.6,128.6,128.5,128.4,80.2,68.0,58.9,53.3,52.7,51.6,48.2,45.3,42.5,42.5,34.7,28.2,27.0,24.7,19.8,19.7.;HRMS(ESI-TOF)forC30H41NO9S2[M+Na]+calcd 646.2115,Fund 646.2115.
实施例23
化合物6a的合成:
空气氛围下,在烧瓶中加入1b(0.2mmol,41.6mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-50℃条件下反应10min,随后往烧瓶中加入5a(0.3mmol,43.3mg,1.5equiv.),反应16小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物6a(产率73%)。(洗脱剂极性:石油醚/乙酸乙酯15:1)。1H NMR(400MHz,CDCl3)δ7.84(d,J=7.4Hz,2H),7.67(d,J=8.2Hz,2H),7.59–7.54(m,1H),7.46–7.40(m,2H),7.19(d,J=8.1Hz,2H),6.74(s,1H),6.53(s,1H),5.35(s,1H),2.36(s,3H).;13C NMR(100MHz,CDCl3)δ191.3,146.2,144.8,135.7,135.1,133.6,129.8,129.3,128.6,128.6,128.5,46.5,21.6.;HRMS(ESI-TOF)Calcd for[C18H15D3O3S2.M+Na]+372.0778,Found:372.0777.
实施例24
化合物6b的合成:
空气氛围下,在烧瓶中加入1b(0.2mmol,41.6mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-50℃条件下反应10min,随后往烧瓶中加入5b(0.3mmol,47.5mg,1.5equiv.),反应16小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物6b(产率55%)。(洗脱剂极性:石油醚/乙酸乙酯15:1)。1H NMR(400MHz,CDCl3)δ7.74(d,J=8.1Hz,2H),7.67(d,J=8.2Hz,2H),7.25–7.16(m,4H),6.72(s,1H),6.51(s,1H),5.33(s,1H),2.41(s,3H),2.35(s,3H).;13C NMR(100MHz,CDCl3)δ190.9,146.3,144.8,144.6,135.7,132.5,129.7,129.3,129.2,128.7,128.4,46.3,21.7,21.6.;HRMS(ESI-TOF)Calcd for[C19H17D3O3S2,M+Na]+386.0934,Found:386.0933.
实施例25
化合物6c的合成:
空气氛围下,在烧瓶中加入1b(0.2mmol,41.6mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-50℃条件下反应10min,随后往烧瓶中加入5c(0.3mmol,52.3mg,1.5equiv.),反应16小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物6c(产率52%)。(洗脱剂极性:石油醚/乙酸乙酯15:1)。1H NMR(400MHz,CDCl3)δ7.83(d,J=8.8Hz,2H),7.67(d,J=8.2Hz,2H),7.18(d,J=8.1Hz,2H),6.89(d,J=8.8Hz,2H),6.71(s,1H),6.49(s,1H),5.32(s,1H),3.86(s,3H),2.35(s,3H).;13C NMR(100MHz,CDCl3)δ189.9,163.9,146.3,144.7,135.7,131.0,129.7,129.1,128.4,127.7,113.8,55.5,46.2,21.5.;HRMS(ESI-TOF)Calcd for[C19H17D3O4S2,M+Na]+402.0884,Found:402.0884.
实施例26
化合物7a的合成:
氮气氛围下,在烧瓶中加入1b(0.2mmol,41.6mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2a(0.3mmol,52.3mg,1.5equiv.),反应10小时后,加入DBU(0.4mmol,60.9mg,2.0equiv.)继续搅拌4小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物7a(产率81%)。(洗脱剂极性:石油醚/乙酸乙酯6:1)。1H NMR(400MHz,CDCl3)δ7.84(s,1H),7.69(d,J=8.2Hz,2H),7.37–7.30(m,3H),7.21(d,J=7.9Hz,4H),4.88(s,2H),3.39(s,2H),2.38(s,3H).;13C NMR(100MHz,CDCl3)δ167.5,147.4,144.1,136.3,135.3,129.7,128.4,128.2,128.1,127.9,127.9,66.8,33.2,21.6.;HRMS(ESI-TOF)Calcd for[C19H17D3O4S2,M+Na]+402.0884,Found:402.0884.
实施例27
化合物7b的合成:
氮气氛围下,在烧瓶中加入1d(0.2mmol,49.5mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2a(0.3mmol,52.2mg,1.5equiv.),反应10小时后,加入DBU(0.4mmol,60.9mg,2.0equiv.)继续搅拌4小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物7b(产率67%)。(洗脱剂极性:石油醚/乙酸乙酯6:1)。1H NMR(400MHz,CDCl3)δ7.78(s,1H),7.67(d,J=8.4Hz,2H),7.38(d,J=8.4Hz,2H),7.29–7.20(m,3H),7.15(d,J=7.0Hz,2H),4.78(s,2H),3.31(s,2H),1.22(s,9H).;13C NMR(100MHz,CDCl3)δ167.5,157.0,147.4,136.1,135.2,128.4,128.1,127.9,127.8,127.8,126.0,66.7,35.1,33.2,30.9.;HRMS(ESI-TOF)Calcd for[C22H23D3O4S2,M+Na]+444.1353,Found:444.1355.
实施例28
化合物7c的合成:
氮气氛围下,在烧瓶中加入1c(0.2mmol,44.3mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2a(0.3mmol,52.2mg,1.5equiv.),反应10小时后,加入DBU(0.4mmol,60.9mg,2.0equiv.)继续搅拌4小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物7c(产率71%)。(洗脱剂极性:石油醚/乙酸乙酯6:1)。1H NMR(400MHz,CDCl3)δ7.82(s,1H),7.73(d,J=8.9Hz,2H),7.37–7.29(m,3H),7.25–7.16(m,2H),6.88(d,J=8.9Hz,2H),4.89(s,2H),3.82(s,3H),3.39(s,2H).;13C NMR(100MHz,CDCl3)δ167.6,163.3,146.8,135.3,130.5,130.3,128.4,128.2,128.1,128.0,114.2,66.8,55.6,33.2.;HRMS(ESI-TOF)Calcdfor[C19H17D3O5S2,M+Na]+418.0833,Found:418.0838.
实施例29
化合物7d的合成:
氮气氛围下,在烧瓶中加入1a(0.2mmol,41.6mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2b(0.3mmol,75.1mg,1.5equiv.),反应10小时后,加入DBU(0.4mmol,60.9mg,2.0equiv.)继续搅拌4小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物7d(产率80%)。(洗脱剂极性:石油醚/乙酸乙酯10:1)。1H NMR(400MHz,CDCl3)δ7.82(s,1H),7.57(d,J=7.8Hz,2H),7.33–7.13(m,10H),7.00(d,J=7.7Hz,2H),6.53(s,1H),3.43(s,2H),2.26(s,3H).;13C NMR(101MHz,CDCl3)δ166.6,147.4,144.0,139.7,136.0,129.6,128.3,127.9,127.8,126.9,77.6,33.5,21.6.;HRMS(ESI-TOF)Calcdfor[C25H21D3O4S2,M+Na]+478.1197,Found:478.1195.
实施例30
化合物7e的合成:
氮气氛围下,在烧瓶中加入1b(0.2mmol,41.6mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2c(0.3mmol,56.5mg,1.5equiv.),反应10小时后,加入DBU(0.4mmol,60.9mg,2.0equiv.)继续搅拌4小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物7e(67%)。(洗脱剂极性:石油醚/乙酸乙酯10:1)。.1H NMR(400MHz,CDCl3)δ7.73(s,1H),7.59(d,J=8.2Hz,2H),7.25–7.18(m,2H),7.18–7.12(m,3H),7.07(d,J=7.0Hz,2H),3.94(t,J=7.1Hz,2H),3.23(s,2H),2.66(t,J=7.1Hz,2H),2.30(s,3H).;13CNMR(100MHz,CDCl3)δ167.6,147.3,144.1,137.5,136.2,129.7,128.9,128.4,128.1,127.7,126.5,65.6,34.7,33.2,21.5.;HRMS(ESI-TOF)Calcd for[C20H19D3O4S2,M+Na]+416.1040,Found:416.1040.
实施例31
合物7f的合成:
氮气氛围下,在烧瓶中加入1b(0.2mmol,41.6mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2d(0.3mmol,50.4mg,1.5equiv.),反应10小时后,加入DBU(0.4mmol,60.9mg,2.0equiv.)继续搅拌4小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物7f(产率70%)。(洗脱剂极性:石油醚/乙酸乙酯8:1)。1H NMR(600MHz,CDCl3)δ7.81(s,1H),7.71(d,J=8.1Hz,2H),7.27(d,J=7.5Hz,2H),3.81(t,J=6.7Hz,2H),3.31(s,2H),2.40(s,3H),1.46–1.39(m,2H),1.30–1.20(m,6H),0.87(t,J=7.1Hz,3H).;13C NMR(150MHz,CDCl3)δ167.7,147.1,144.0,136.4,129.6,128.2,128.1,65.3,33.3,31.3,28.2,25.3,22.4,21.5,13.9.;HRMS(ESI-TOF)Calcdfor[C18H23D3O4S2,M+Na]+396.1353,Found:396.1355.
实施例32
化合物7g的合成:
氮气氛围下,在烧瓶中加入1p(0.2mmol,71.3mg,1equiv.),DABCO(0.02mmol,2.24mg,10mol%)和二氯甲烷(2mL),将反应体系在-30℃条件下反应10min,随后往烧瓶中加入2a(0.3mmol,52.3mg,1.5equiv.),反应10小时后,加入DBU(0.4mmol,60.9mg,2.0equiv.)继续搅拌4小时,TLC检测反应结束后,加入硅胶,减压条件下去除溶剂后,柱层析纯化得到产物7g(产率75%)。(洗脱剂极性:石油醚/乙酸乙酯6:1)。1H NMR(400MHz,CDCl3)δ7.86(s,1H),7.72(d,J=8.9Hz,2H),7.37–7.28(m,3H),7.25–7.15(m,2H),6.87(d,J=8.9Hz,2H),4.88(s,2H),3.82(s,3H),3.40(s,2H),2.88(t,J=7.4Hz,2H),1.71–1.63(m,2H),1.41–1.24(m,18H),0.88(t,J=6.8Hz,3H).;13C NMR(100MHz,CDCl3)δ167.7,163.3,145.9,135.3,130.7,130.2,128.4,128.1,127.9,114.2,66.8,55.6,34.9,33.3,31.9,30.5,29.6,29.5,29.4,29.3,29.0,28.4,22.7,14.1.;HRMS(ESI-TOF)Calcdfor[C30H42O5S2,M+Na]+569.2366,Found:569.2370.
Claims (10)
3.如权利要求1或2所述的合成方法,其特征在于路易斯碱催化剂为DABCO、PPh3、DMAP或Quinine,催化剂的用量为式(1)所示化合物用量的1~15mol%,优选为10mol%。
4.如权利要求2所述的合成方法,其特征在于所述碱为DBU或i-Pr2Net。
5.如权利要求1所述的合成方法,其特征在于有机溶剂是二氯甲烷、乙酸乙酯、氯仿、二甲亚砜、N,N-二甲基甲酰胺、乙腈或四氢呋喃,优选为二氯甲烷。
6.如权利要求1所述的合成方法,其特征在于反应温度为-70-30℃。
7.如权利要求1所述的合成方法,其特征在于如式(1)所示的化合物与如式(2)所示的化合物的摩尔比例为1.0:1.0-1.0:2.0,优选为1.0:1.5。
8.如权利要求4所述的合成方法,其特征在于碱的用量为硫代硫酸盐化合物的1.0-3.0当量。
9.如权利要求1所述的合成方法,其特征在于反应后处理的方法为:反应结束后,将反应液浓缩,进行柱层析,以石油醚与乙酸乙酯混合液作为洗脱剂,收集含目标化合物的洗脱液,浓缩蒸馏并干燥,得到如式(3)所示的化合物。
10.如权利要求9所述的合成方法,其特征在于石油醚与乙酸乙酯混合液的体积比为3-20:1。
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